Method for conducting catalytic hydrogenation on nitrogen-containing unsaturated heterocyclic compound

A heterocyclic compound and unsaturated technology, which is applied in the field of catalytic hydrogenation, can solve the problems that the catalytic effect needs to be improved, and the scope of application of the catalyst substrate is limited.

Active Publication Date: 2019-12-20
TSINGHUA UNIV
View PDF1 Cites 1 Cited by
  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

[0003] There are currently reports on the use of cheap metal catalysts, such as iron catalysts or cobalt catalysts, to catalyze the hydrogenation of unsaturated heterocyclic compounds (J.Am.Chem.Soc.2014,136,8564; ACS Catal.2015,5,6350; Angew.Chem .Int.Ed.2017,56,3216), but the scope of application of the substrates of the above catalysts is limited, and the catalytic effect needs to be improved

Method used

the structure of the environmentally friendly knitted fabric provided by the present invention; figure 2 Flow chart of the yarn wrapping machine for environmentally friendly knitted fabrics and storage devices; image 3 Is the parameter map of the yarn covering machine
View more

Image

Smart Image Click on the blue labels to locate them in the text.
Viewing Examples
Smart Image
  • Method for conducting catalytic hydrogenation on nitrogen-containing unsaturated heterocyclic compound
  • Method for conducting catalytic hydrogenation on nitrogen-containing unsaturated heterocyclic compound
  • Method for conducting catalytic hydrogenation on nitrogen-containing unsaturated heterocyclic compound

Examples

Experimental program
Comparison scheme
Effect test

preparation example Construction

[0047]The manganese catalyst that the present invention adopts is NNP type pincer manganese catalyst, and it has cheap, easy to get, the advantage of low toxicity with respect to noble metal catalyst; With respect to existing cheap metal iron catalyst or cobalt catalyst, has bottom It has the advantages of wide material applicability and high yield of target products; compared with PNP-type pincer manganese catalyst, it has stronger electron donating ability and smaller steric hindrance, so it shows higher reactivity in a series of hydrogenation reactions , the target product yield can reach up to 99%. In the present invention, the manganese catalysts [Mn]-1, [Mn]-3 and [Mn]-4 are preferably synthesized by reference method (Chem.Sci.2017,8,3576; J.Am.Chem.Soc. 2017,139,11941; Angew.Chem.Int.Ed.2018,57,13439), the preparation method of the manganese catalyst [Mn]-2 preferably comprises the following steps:

[0048] Mix 2-chloroethylamine hydrochloride, trimethylchlorosilane, t...

Embodiment 1

[0072] Preparation has the manganese catalyst of structure shown in formula II, i.e. manganese catalyst [Mn]-2, comprises the following steps:

[0073] (1) Synthesis of 2-chloro-N,N-bis(trimethylsilyl)ethylamine

[0074]

[0075] Add 2-chloroethylamine hydrochloride (4.6g, 40mmol), triethylamine (NEt 3 , 18mL, 132mmol) and dichloromethane 50mL, a dichloromethane solution (20mL) of trimethylchlorosilane (TMSCl, 90mmol, 9.8g, 11.4mL) was added to the resulting system, and the reaction was stirred at room temperature for 12h; the reaction ended Afterwards, excess triethylamine, trimethylchlorosilane and dichloromethane were removed under reduced pressure, 60 mL of n-hexane was added to the resulting residue, stirred at room temperature for 30 min, and NEt was removed by filtration. 3 HCl, use a rotary evaporator to carry out rotary evaporation to the filtrate to remove n-hexane, and then use an oil pump to carry out vacuum distillation, and the obtained fraction is the target...

Embodiment 2

[0095] In a glove box filled with argon, potassium tert-butoxide (5.6mg, 0.05mmol) and manganese catalyst (0.005mmol) were successively added to a 4mL glass bottle with a stirrer, and the manganese catalysts were represented by formulas I to IV The manganese catalyst of the shown structure is respectively denoted as manganese catalyst [Mn]-1, [Mn]-2, [Mn]-3, [Mn]-4), tetrahydrofuran (0.5mL) and quinoline (0.25mmol), Cover the bottle cap, insert a needle with a vent hole on the bottle cap (the length is 3cm, and the aperture of the vent hole is 1mm), the glass bottle is put into the autoclave, and then the autoclave is taken out from the glove box, Replace the argon (3×10bar) in the autoclave with hydrogen, then fill it with 80bar hydrogen, and react at 120°C for 16h; GC quantified and separated by column chromatography to obtain the target product.

[0096] Taking the manganese catalyst [Mn]-1 as an example, the reaction process is as follows:

[0097]

[0098] The struct...

the structure of the environmentally friendly knitted fabric provided by the present invention; figure 2 Flow chart of the yarn wrapping machine for environmentally friendly knitted fabrics and storage devices; image 3 Is the parameter map of the yarn covering machine
Login to view more

PUM

No PUM Login to view more

Abstract

The invention provides a method for conducting catalytic hydrogenation on a nitrogen-containing unsaturated heterocyclic compound, and belongs to the technical field of catalytic hydrogenation. The provided method for conducting catalytic hydrogenation on the nitrogen-containing unsaturated heterocyclic compound comprises the following step: in the presence of hydrogen and a manganese catalyst, with the nitrogen-containing unsaturated heterocyclic compound as a substrate, carrying out a hydrogenation reaction. According to the method for conducting catalytic hydrogenation on the nitrogen-containing unsaturated heterocyclic compound, he adopted manganese catalyst is an NNP-type pincer manganese catalyst, has the advantages of being cheap, easy to obtain and low in toxicity compared with noble metal catalysts, has the advantages of being wide in substrate applicability and high in target product yield compared with an existing cheap metal iron catalyst or cobalt catalyst, and is higher in electron donating ability and smaller in steric hindrance compared with a PNP-type pincer manganese catalyst, and thus shows higher reaction activity in a series of hydrogenation reactions, and thetarget product yield is up to 99%.

Description

technical field [0001] The invention relates to the technical field of catalytic hydrogenation, in particular to a method for catalytic hydrogenation of nitrogen-containing unsaturated heterocyclic compounds. Background technique [0002] The hydrogenation reaction of unsaturated heterocyclic compounds is a very important reaction in organic synthesis. It can conveniently synthesize various compounds containing saturated heterocyclic structures, and provides a material basis for active pharmaceutical molecules with saturated heterocyclic structures as the core skeleton. . The hydrogenation of unsaturated heterocyclic compounds destroys its own aromaticity. Compared with the hydrogenation of common unsaturated substrates such as ketones and imines, it is necessary to overcome the aromatic stabilization energy of the heterocyclic ring itself. Therefore, the hydrogenation of unsaturated heterocyclic compounds is relatively more difficult. Thanks to the development of noble me...

Claims

the structure of the environmentally friendly knitted fabric provided by the present invention; figure 2 Flow chart of the yarn wrapping machine for environmentally friendly knitted fabrics and storage devices; image 3 Is the parameter map of the yarn covering machine
Login to view more

Application Information

Patent Timeline
no application Login to view more
Patent Type & Authority Applications(China)
IPC IPC(8): C07D215/06C07D215/18C07D217/02C07D471/04C07D241/38C07D221/10C07D221/12C07D219/02C07F13/00B01J31/22
CPCB01J31/1815B01J31/20B01J31/2409B01J2231/646B01J2531/72C07D215/06C07D215/18C07D217/02C07D219/02C07D221/10C07D221/12C07D241/38C07D471/04C07F13/005
Inventor 刘强王玉杰
Owner TSINGHUA UNIV
Who we serve
  • R&D Engineer
  • R&D Manager
  • IP Professional
Why Eureka
  • Industry Leading Data Capabilities
  • Powerful AI technology
  • Patent DNA Extraction
Social media
Try Eureka
PatSnap group products

Browse by: Latest US Patents, China's latest patents, Technical Efficacy Thesaurus, Application Domain, Technology Topic.

© 2024 PatSnap. All rights reserved.Legal|Privacy policy|Modern Slavery Act Transparency Statement|Sitemap